Deprotonation in mixed-valent diiron(II, III) complexes with aniline or benzimidazole ligands - Archive ouverte HAL Access content directly
Journal Articles Inorganic Chemistry Year : 2015

Deprotonation in mixed-valent diiron(II, III) complexes with aniline or benzimidazole ligands

Abstract

We have previously investigated cis/trans isomerization processes in phenoxido-bridged mixed-valent Fe$^{II}$Fe$^{III}$ complexes that contain either one aniline or one anilide ligand. In this work, we compare the properties of similar complexes bearing one terminal protic ligand, either aniline or 1H-benzimidazole. Whatever the ligand, $^1$H NMR spectroscopy clearly evidences that the complexes are present in CH$_3$CN as a mixture of cis- and trans-isomers in a close to 1:1 ratio. We show here that addition of NEt$_3$ indeed allows the deprotonation of these ligands, the resulting complexes bearing either anilide or benzimidazolide that are coordinated to the ferric site. The latter are singular examples of a high-spin ferric ion coordinated to a benzimidazolide ligand. Whereas the trans-isomer of the anilide complex is the overwhelming species, benzimidazolide species are mixtures of cis- and trans-isomers in equal proportions. Moreover, cyclic voltammametry studies show that Fe$^{II}$Fe$^{III}$ complexes with 1H-benzimidazole are more stable than their aniline counterparts, whereas the reverse is observed for the deprotonated species.
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Dates and versions

hal-01211562 , version 1 (05-10-2015)

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Eric Gouré, Michaël Carboni, Angélique Troussier, Patrick Dubourdeaux, Martin Clémancey, et al.. Deprotonation in mixed-valent diiron(II, III) complexes with aniline or benzimidazole ligands. Inorganic Chemistry, 2015, 54 (13), pp.6257-6266. ⟨10.1021/acs.inorgchem.5b00449⟩. ⟨hal-01211562⟩
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